Sulfate adsorption at buried mineral/solution interfaces is of great interest in geochemistry and atmospheric aerosol chemistry due to the sulfate anion's environmental ubiquity and the wide role of physical and chemical phenomena that it impacts. Here we present the first application of total internal reflection-Raman (TIR-Raman) spectroscopy, a surface-sensitive spectroscopy, to probe sulfate ion behavior at the buried hematite/solution interface. Hematite is the most thermodynamically stable iron oxide polymorph and as such is widely found in nature. Our results demonstrate the feasibility of a TIR-Raman approach to study simple, inorganic anion adsorption at buried interfaces. Moreover, our data suggest that inner-sphere sulfate adsorption proceeds in a bidentate fashion at the hematite surface. These results help clarify long-standing questions as to whether sulfate forms inner-sphere adsorption complexes at hematite surfaces in a mono- or bidentate fashion based on attenuated total reflection-infrared (ATR-IR) observations. Our results are discussed with perspective to this debate and the applicability of TIR-Raman spectroscopy to address ambiguities of ion adsorption to mineral surfaces. (C) 2013 Elsevier Inc. All rights reserved.